Chemical Equilibrium -

Factors Affecting
Chemical Equilibrium

Dr Ernest C. Agwamba
OUTLINES
• Types of Chemical Equilibrium
• Factors Affecting Chemical Equilibrium
• Examples
• Importance
• Problems
 What Is Chemical Equilibrium?
• Chemical equilibrium refers to when the rate
of the forward reaction is equal to the rate of
the reverse reaction, the state of chemical
equilibrium is achieved by the system.

• This refers to the state of a system in which

the concentration of the reactant and the
concentration of the products do not change
with time, and the system does not display
any further change in properties.
• When there is no further change in the
concentrations of the reactants and the
products due to the equal rates of the
forward and reverse reactions, the system is
said to be in a state of dynamic equilibrium.
State of Chemical Equilibrium
Why Is Chemical Equilibrium Called
Dynamic Equilibrium?
• The stage at which the rate of the forward
reaction is equal to the rate of the backward
reaction is called an equilibrium stage.
• At this point, the number of reactant
molecules converting into products and
product molecules into reactants is the
same.
• The same equilibrium can be carried out with
the same reactants anywhere with similar
conditions with continuous interchanging of
molecules, and hence chemical equilibrium
is dynamic.
Conditions for Chemical
Equilibrium
i. The systems must be closed, meaning no substance
can enter or leave the system.
ii. Equilibrium is a dynamic process. Even though we
don’t necessarily see the reaction, both forward and
reverse reaction are taking place.
iii. The rate of the forward and reverse reaction must be
equal.
iv. The amount of the reactant and products do not
have to equal. However, after equilibrium is
attained, the amount of the reactant and Product
will remain unchanged.
Types of Chemical Equilibrium
• There are two types of chemical equilibrium:
• Homogeneous Equilibrium
• In this type, the reactants and the products of
chemical equilibrium are all in the same
phase. Homogenous equilibrium can be further
divided into two types:
• Heterogeneous Equilibrium
• In this type, the reactants and the products of
chemical equilibrium are present in different
phases. A few examples of heterogeneous
equilibrium are given below:

• Reactions in which the number of molecules of the

products is equal to the number of molecules of the
reactants. For example,
• Thus, the different types of chemical equilibrium
are based on the phase of the reactants and
products.

• Reactions in which the number of molecules of the

products is not equal to the total number of reactant
molecules. For example,
Equilibrium Constant
• Consider the hypothetical reaction in which reactant A and B react to form
products C and D. This equilibrium can be shown below, where the lower
letter represent the coefficient of each substance.

• As we have established, the rate of the forward and reverse reaction are the
same at equilibrium and so the concentrations of all of the substance are
constant.
• Therefore, the ratio of the concentration for any given reaction at
equilibrium maintains a constant value.
• The equilibrium constant (Keq) is the ratio of the mathematical product of
the products of a reaction to the mathematical product of the concentration
of the reactant of the reaction.
• Each concentration is raised to the power of its coefficient in the balanced
chemical equation.
Equilibrium Constant…..contd.
• The concentration of each substance, indicated by the square bracket around
the formula, are measured in molarity units (mol/L).

• The value of the Keq for any reaction is only determined by experiment. As
detailed in the above section, the position of equilibrium for a given reaction
does not depend on the starting concentrations and so the value of the
equilibrium constant is truly constant. It depends on temperature.

• Therefore,
• when Keq > 1 : numerator is larger than the denominator, so the products are
favoured. This means, the concentration of its products are greater than that
of the reactants.
• When Keq < 1 : then the reactants are favoured because the denominator is
larger the numerator (products).
• When Keq = 1: the concentration of the reactant and products are
approximately equal
Reaction Quotient (Q)
• The reaction quotient (Q), is used when questioning if we are at
equilibrium. The calculation for Q is exactly the same as for Keq but we
can only use Keq when we know we are at equilibrium. Comparing Q
and Keq allows the direction of the reaction to be predicted.
• Q = Keq : equilibrium
• Q < Keq : reaction proceeds to the right to form more products and
decrease amount of the reactants so value of Q will increase.
• Q > Keq : reaction proceeds to the left to form more reactants and
decrease amount of products so value of Q will decrease.
Factors Affecting Chemical
Equilibrium
• According to Le-Chatelier’s principle, if
there is any change in the factors
affecting the equilibrium conditions, the
system will counteract or reduce the
effect of the overall transformation. This
principle applies to both chemical
and physical equilibrium.
• There are several factors like temperature,
pressure and concentration of the system
that affect equilibrium. Some important
factors affecting chemical equilibrium are
explained below.
Change in Concentration
• The concentration of the reactants or
products added is relieved by the
reaction, which consumes the
substance that is added.
• The concentration of reactants or
products removed is relieved by the
reaction, which is in the direction that
replenishes the substance which is
removed.
• When the concentration of the reactant
or product is changed, there is a change
in the composition of the mixture in
chemical equilibrium.
Change in Pressure
• Change in pressure happens due to the change in the
volume. If there is a change in pressure, it can affect the
gaseous reaction as the total number of gaseous
reactants and products are now different. According to
Le Chatelier’s principle, in heterogeneous chemical
equilibrium, the change of pressure in both liquids and
solids can be ignored because the volume is
independent of pressure.
Change in Temperature
• The effect of temperature on chemical equilibrium
depends upon the sign of ΔH of the reaction and
follows Le-Chatelier’s Principle.
• As temperature increases, the equilibrium
constant of an exothermic reaction decreases.
• In an endothermic reaction, the equilibrium constant
increases with an increase in temperature.
• Along with the equilibrium constant, the rate of
reaction is also affected by the change in
temperature.
• As per Le-Chatelier’s principle, the equilibrium shifts
towards the reactant side when the temperature
increases in the case of exothermic reactions;
for endothermic reactions, the equilibrium shifts
towards the product side with an increase in
temperature.
Effect of a Catalyst
• A catalyst does not affect the chemical equilibrium, it
only speeds up a reaction. In fact, the catalyst equally
speeds up the forward as well as the reverse reaction.
This results in the reaction reaching its equilibrium faster.
• The same amount of reactants and products will be
present at equilibrium in a catalysed or non-catalysed
reaction. The presence of a catalyst only facilitates the
reaction to proceed through a lower-energy transition
state of reactants to products.
Effect of Addition of an Inert Gas
• When an inert gas like argon is added to a constant
volume, it does not take part in the reaction, so the
equilibrium remains undisturbed. If the gas added is a
reactant or product involved in the reaction, then the
reaction quotient will change.
 Examples of Chemical Equilibrium
• In chemical reactions, reactants are converted into
products by the forward reaction, and the products
may be converted into reactants by the backward
reaction. The two states, reactants and products,
are different in composition.
• After some time of the start of the reaction, the rate
of the forward and the backward reactions may
become equal.
• Then, the number of reactants converted will be
formed again by the reverse reaction such that the
concentration of reactants and products does not
change anymore. Hence, the reactants and
products are in chemical equilibrium.
Importance of Chemical
Equilibrium
• It is useful in many industrial processes, like
• Preparation of ammonia by Haber’s process: In this
process, nitrogen combines with hydrogen to form
ammonia; the yield of ammonia is more at low
temperature, high pressure and in the presence of iron
as a catalyst.
• Preparation of sulphuric acid by contact process: In this
process, the fundamental reaction is the oxidation of
sulphur dioxide into sulphur trioxide. This involves
chemical equilibrium.
 Problems on Chemical Equilibrium
1. The equilibrium constant KP for the reaction N2 (g) + 3H2 (g) ⇌ 2NH3 (g) is 1.6
× 10-4 atm-2 at 400oC. What will be the equilibrium constant of the Chemical
equilibrium at 500oC if the heat of the reaction at this temperature range is -
25.14 kcal?
Solution 1:
To solve this problem, we can use the van’t Hoff equation, which describes the temperature dependence of the
equilibrium constant. The equation is:

• The initial equilibrium constant, K1​, is 1.6×10−41.6×10−4 atm-2 at an initial temperature, T1​, of 400°C (or 673.15
K in Kelvin).
• The heat of the reaction, ΔH, is -25.14 kcal, which is equivalent to -105100 J/mol (since 1 kcal = 4184 J).
• The gas constant, R, is 8.314 J/(mol·K).
• The final temperature, T2​, is 500°C (or 773.15 K in Kelvin).
Substituting these values into the Van’t Hoff equation, we can solve for the final equilibrium constant, K2​.
K2 = KP2 = 1.462 × 10-5 atm-2
3. A vessel at 1000 K contains CO2 with a pressure of 0.5
atm. Some of the CO2 is converted into CO on the
addition of graphite. If the total pressure at equilibrium
is 0.8 atm, the value of K is.
Solution
Revision Questions
• Q1. What is the effect of temperature on the equilibrium constant during an exothermic reaction?

• Q2. What is the effect of a catalyst on a chemical equilibrium?

• Q3. What is the effect of the addition of inert gas during chemical equilibrium?

• Q4. What is meant by the forward reaction?

• Q5. What is meant by the backward reaction?

Revision Questions
• Q1. What is the effect of temperature on the equilibrium constant during an exothermic reaction?
Answer: With the increase in temperature, the equilibrium constant decreases during an
exothermic reaction.

• Q2. What is the effect of a catalyst on a chemical equilibrium?

Answer: A catalyst has no effect on the chemical equilibrium.

• Q3. What is the effect of the addition of inert gas during chemical equilibrium?
Answer: There is no effect on chemical equilibrium with the addition of inert gas.

• Q4. What is meant by the forward reaction?

Answer: A reaction in which the reactants are converted to products is called a forward
reaction.

• Q5. What is meant by the backward reaction?

Answer: A reaction in which the products are converted back to reactants is called the
backward reaction.